(1) Under the protection of inert gas, mixing acrylonitrile and N- (3-aminopropyl) cyclohexylamine, then adding an allylamine catalyst for reaction, and after the reaction is finished, carrying out reduced pressure distillation to recover unreacted acrylonitrile and the catalyst to obtain an intermediate;

(2) And (2) mixing the intermediate prepared in the step (1) with a solvent and a supported rhodium catalyst, then introducing hydrogen to carry out hydrogenation reaction, decompressing and distilling to recover ethanol after the reaction is finished, and then filtering and drying to obtain the cyclohexylamine derivative shown in the formula (I).

In step (1) of the present invention, the molar ratio of acrylonitrile to N- (3-aminopropyl) cyclohexylamine is (1.8-2.4): 1, preferably (2-2.2): 1;

preferably, when the acrylonitrile is mixed with the N- (3-aminopropyl) cyclohexylamine, the acrylonitrile is added into the N- (3-aminopropyl) cyclohexylamine, more preferably, the acrylonitrile is continuously added, and further preferably, dropwise added, and the adding time is 1-1.8h; the addition time is included in the reaction time.

In step (1) of the present invention, the allylamine catalyst is one or more selected from the group consisting of monoallylamine, diallylamine, and triallylamine, preferably monoallylamine;

preferably, the molar ratio of the allyl amine catalyst to the N- (3-aminopropyl) cyclohexylamine is (0.01-2): 1, preferably (0.05-0.1): 1.

in the step (1), the reaction is carried out at the temperature of 40-100 ℃, preferably 60-80 ℃ for 12-36h, preferably 18-24h; more preferably, the reaction is carried out under reflux.

In the step (1) of the invention, the preferable conditions of reduced pressure distillation are that the pressure is 2-6kPa, and the temperature is 25-45 ℃; preferably, after the unreacted acrylonitrile and the catalyst are recovered by reduced pressure distillation, the post-treatment processes such as filtration and drying are all conventional operations in the field, and no specific requirement is made, for example, the drying can be carried out at 60-80 ℃ in vacuum to constant weight.

In step (1) of the present invention, the inert gas is selected from argon or nitrogen, preferably nitrogen.

In the step (1) of the invention, the prepared intermediate has a structure shown in the following formula (II),

in step (2) of the present invention, the supported rhodium catalyst has a rhodium (Rh) content of 2 to 7wt%, preferably 3 to 4wt%, based on the total weight of the supported rhodium catalyst;

preferably, the rhodium-loaded catalyst, the carrier is selected from one or more of rare earth, diatomite, alumina, activated carbon, silica-alumina oxide and spinel, more preferably alumina;

preferably, the supported rhodium catalyst is added in an amount of (0.5-5) wt%, preferably (1.5-2) wt% of the intermediate.

In step (2) of the present invention, the solvent is selected from one or more of cyclohexane, tetrahydrofuran, dichloromethane, cyclohexylamine, methanol, isopropanol, ethanol, and n-butanol, and tetrahydrofuran is more preferred;

preferably, the solvent is used in an amount of 20 to 60wt%, more preferably 30 to 40wt%, based on 100% by weight of the total weight of the intermediate and the solvent.

In the step (2) of the invention, the introduction amount of hydrogen is controlled by the reaction pressure, i.e. the hydrogenation reaction pressure is maintained within the required range by adjusting the introduction amount of hydrogen.

In step (2) of the present invention, the reaction is carried out at a pressure of 4 to 12MPa (absolute pressure), preferably 6 to 10MPa (absolute pressure), at a temperature of 100 to 180 ℃, preferably 120 to 160 ℃, for a time of 2 to 6 hours, preferably 4 to 5 hours.

In the step (2), ethanol is recovered by reduced pressure distillation, filtered and dried, which is a conventional operation in the field and does not need to be specifically required. In some examples, the reduced pressure distillation is preferably at a pressure of 3 to 6kPa, at a temperature of 25 to 45 ℃; the drying is preferably carried out at 60-80 ℃ under vacuum to constant weight.

The invention also provides an epoxy resin composition, which comprises an A-component epoxy resin and a B-component epoxy curing agent;

the A component comprises at least one epoxy resin;

the component B comprises:

b1 cyclohexylamine derivative (N, N' -bis (3-aminopropyl) -3-aminopropylcyclohexylamine) represented by the above formula (I);

b2 at least one latent amine curing agent;

b3 at least one alicyclic amine;

b4 at least one polyetheramine.

Further, in the epoxy resin composition of the present invention, the viscosity of the B-component epoxy curing agent is 20 to 1000cps, preferably 50 to 200cps.

Further, the epoxy resin composition of the invention has a mass ratio of the component A epoxy resin to the component B epoxy curing agent of 100: (20-50), preferably 100: (30-40).

Further, in the epoxy resin composition of the present invention, the amount of B1 to B4 in the component B epoxy hardener composition is the cyclohexylamine derivative represented by the formula (I): latent amine curing agent: alicyclic amine: the mass ratio of the polyether amine is 1: (2-6): (4-8): (3-6), preferably 1: (2-4): (4-6): (3-5).

Further, the epoxy resin composition of the present invention is an epoxy resin composition, wherein the epoxy resin is one or more selected from bisphenol a type epoxy resin, bisphenol F type epoxy resin, alicyclic glycidyl ether type epoxy resin and glycidyl amine type epoxy resin, preferably one or more selected from bisphenol a type epoxy resin and bisphenol F type epoxy resin;

more preferably, the bisphenol a type epoxy resin is DER 331, and the bisphenol F type epoxy resin is DER 354;

more preferably, the epoxy resin is a mixture of bisphenol a epoxy resin and bisphenol F epoxy resin, and the mass ratio of the mixture of bisphenol a epoxy resin and bisphenol F epoxy resin is preferably 1: (0.1-2), preferably 1: (0.4-0.8);

the solid latent amine curing agent is one or a combination of two of dicyandiamide and diaminodiphenyl sulfone, preferably dicyandiamide;

the alicyclic amine is selected from one or more of diaminodicyclohexyl methane, isophorone diamine, methyl cyclohexane diamine, dimethyl diaminodicyclohexyl methane and 1,3-cyclohexane dimethylamine, and preferably one or two of diaminodicyclohexyl methane and isophorone diamine;

the polyether amine is selected from one or more of D230, wanamine 8100, D400, T403, D2000 and the like, and is preferably selected from the group consisting of Wanamine 8100 and D230.

The epoxy resin composition of the invention, the component A optionally comprises an epoxy diluent and a silane coupling agent;

the epoxy diluent is selected from one or more of 1,4-butanediol diglycidyl ether, alkyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, glycerol glycidyl ether and the like, preferably one or two of 1,4-butanediol diglycidyl ether and benzyl glycidyl ether;

the silane coupling agent is selected from one or more of KH550, KH560, KH570 and KBM403, preferably from one or more of KH550, KH560 and KBM 403;

preferably, in the component A, the ratio of epoxy resin to epoxy diluent is as follows: the mass ratio of the silane coupling agent is (1-3): (0.05-0.3): (0.01-0.1), preferably (1.4-1.8): (0.1-0.2): (0.02-0.04). The invention also provides a preparation method of the epoxy resin composition, which comprises the following steps:

1) Preparing the epoxy resin of the component A: uniformly mixing the epoxy resin with an optional epoxy diluent and an optional silane coupling agent;

2) Preparing a component B epoxy curing agent: mixing a cyclohexylamine derivative shown in a formula (I) with a latent amine curing agent, then adding the mixture into alicyclic amine at the temperature of 20-60 ℃, uniformly mixing, adding polyether amine, and mixing to obtain a component B epoxy curing agent;

3) And mixing the epoxy resin of the component A with the epoxy curing agent of the component B to obtain the epoxy resin composition.

In the preparation method, when the cyclohexylamine derivative in the step 2) is mixed with the latent amine curing agent, the cyclohexylamine derivative and the latent amine curing agent are preferably mixed by a three-roll grinder for 2 to 4 times;

when the mixture is mixed with alicyclic amine, a high-speed stirrer is adopted to stir and disperse for 1-3h until the mixture is completely dissolved, and uniform and transparent mixed liquid is formed.

In some examples, the preferable method in step 2) is: the weight ratio of the cyclohexylamine derivative to the latent amine curing agent is 1: (2-6) mixing, mixing for 2-4 times by a three-roll mill, and then adding the mixture into the alicyclic amine at 20-60 ℃, wherein the mass ratio of the cyclohexylamine derivative to the alicyclic amine is 1: (4-8), mixing at room temperature to form a uniform and transparent mixed solution, and then adding polyether amine, wherein the mass ratio of the cyclohexylamine derivative to the polyether amine is 1: and (3-6), uniformly mixing to obtain the component B epoxy curing agent.

In the preparation method, the mixing operation in the step 3) is carried out, the mixing temperature is 20-30 ℃, and the mixing time is 10-30min.

The invention also provides the application of the epoxy resin composition as a resin matrix of the liquid molding composite material, can be applied to the field of automobile lightweight composite materials, and has the advantages of low-temperature rapid curing, high heat resistance, good mechanical properties (high strength) and the like.

Preferably, the liquid molding method includes resin transfer molding RTM, wet molding WCM, winding molding, infusion molding, and the like.

Preferably, the curing temperature of the epoxy resin composition is 70-100 ℃, preferably 80-100 ℃ and the curing time is 2-60min, preferably 10-30min, in the liquid molding process.

The epoxy resin cured product prepared by curing the epoxy resin composition has the glass transition temperature (Tg) of 80-140 ℃, the tensile strength of 70-100MPa, the bending strength of 120-160MPa and the elongation at break of 3-5%.

Compared with the prior art, the invention has the beneficial effects that:

(1) According to the invention, the cyclohexylamine derivative simultaneously containing primary amine, secondary amine and tertiary amine groups is introduced into the epoxy resin composition and is matched with the latent amine curing agent for use, so that the reaction temperature of the latent amine curing agent can be reduced (from above 120 ℃ to 70-100 ℃), and the obtained epoxy cured material also has high mechanical properties and glass transition temperature. As the primary amine group in the cyclohexylamine derivative can form a hydrogen bond with groups such as cyano-group, sulfuryl group and the like in the latent amine curing agent, the compatibility and solubility of the latent amine curing agent and the liquid curing agent are improved, on one hand, the problem of the compatibility of the latent amine curing agent and the epoxy resin is solved, and on the other hand, the mechanical property of the cured epoxy resin is improved; secondary amine groups in the cyclohexylamine derivatives can form a linear structure with the epoxy resin, and the toughness and the mechanical property of a cured product are improved; the tertiary amine group has a catalytic effect, the reaction temperature of the latent amine curing agent is reduced by activation, and the post-curing degree and the low-temperature reaction speed of the epoxy cured material are improved; the latent amine curing agent component prolongs the low-temperature operation time and improves the heat resistance of the cured product.

(2) The curing agent disclosed by the invention adopts polyether amine and alicyclic amine as main curing agents, has low viscosity, can well dissolve the latent amine curing agent, and forms uniform and stable liquid. Meanwhile, the compound can play a role in concerted catalysis with tertiary amine in the cyclohexylamine derivative with a special structure, so that the curing reaction speed is improved, and the compound is matched with a curing agent component to realize the improvement of heat resistance and mechanical property in a concerted manner.

Drawings

FIG. 1 is an IR spectrum of an intermediate represented by the formula (II) in example 1;

FIG. 2 is an infrared spectrum of a cyclohexylamine derivative represented by the formula (I) in example 1.

Detailed Description

The present invention is further illustrated by the following specific examples, which are intended to be illustrative only and not to limit the scope of the invention.

1. The main raw materials and sources in the examples are detailed in Table 1.

TABLE 1 raw materials and sources

Other raw materials were all purchased from the market unless otherwise stated in table 1.

2. The performance test method comprises the following steps:

viscosity test method: testing by adopting a Bohler flying DV-II type rotational viscometer;

gel time test method: a hot plate method is adopted, the thickness of the resin is 1mm, and a stirring and wire drawing method is adopted to judge gel points;

the infrared spectrum testing method comprises the following steps: measuring with PerkinElmer Frontier Fourier transform infrared spectrometer in the range of 0-4000cm^-1 Scanning times are 8 times;

the mechanical property testing method comprises the following steps: curing the epoxy composition at the temperature of 80 ℃/6h to prepare a mechanical property test sample strip, and testing the mechanical property test sample strip by using a universal material testing machine of Instron company in America; the fracture toughness KIC test is completed according to the test of ASTM D5045-99;

DSC measurement glass transition temperature: the conditions are room temperature-300 deg.C, heating rate of 10 deg.C/min.

Example 1

Preparing cyclohexylamine derivatives of formula (I):

(1) Slowly and dropwise adding acrylonitrile into N- (3-aminopropyl) cyclohexylamine under the conditions of room temperature, nitrogen protection and stirring, wherein the molar ratio of the acrylonitrile to the N- (3-aminopropyl) cyclohexylamine is 2:1, the dropping time is 1h, thenThen adding mono allyl amine, wherein the mol ratio of the mono allyl amine to the N- (3-aminopropyl) cyclohexylamine is 0.05:1, controlling the temperature to carry out reflux reaction for 18h at 60 ℃, after the reaction is finished, carrying out reduced pressure distillation at 2kPa and 25 ℃ to recover unreacted acrylonitrile and a catalyst, namely, allyl amine, filtering and separating a product, and carrying out vacuum drying at 60 ℃ to constant weight to obtain an intermediate. Intermediate structure was tested by infrared spectroscopy (as shown in figure 1): 3370cm^-1 Is the N-H stretching vibration peak of secondary amine, 2200cm^-1 Is located at 1576cm and is a characteristic absorption peak of a nitrile group^-1 The peak is a bending vibration absorption peak of secondary amine, and a characteristic peak of primary amine in cyclohexylamine disappears, indicating that the intermediate has a structure shown in a formula (II).

(2) Mixing the intermediate with Rh/Al₂ O₃ A supported catalyst (Rh loading of 3 wt%) was mixed with tetrahydrofuran, wherein the catalyst amount was 1.5wt% of the intermediate; the concentration of tetrahydrofuran was 30wt% based on the total weight of intermediate and tetrahydrofuran; then introducing hydrogen to maintain the system pressure at about 6MPa, carrying out hydrogenation reaction for 4h at the temperature of 120 ℃ and the pressure of 6MPa, carrying out reduced pressure distillation at the temperature of 3kPa and 25 ℃ to recover tetrahydrofuran after the reaction is finished, then carrying out filtration separation, and finally carrying out vacuum drying at the temperature of 60 ℃ to constant weight to obtain the cyclohexylamine derivative product. The product structure was tested by infrared spectroscopy (as shown in figure 2): 3280-3380cm^-1 The double peak is the N-H stretching vibration peak of primary amine, 1553cm^-1 A bending vibration absorption peak at a secondary amine of 2200cm^-1 The characteristic absorption peak of nitrile group disappears, and the characteristic peak of primary amine obtained by hydrogenation appears, which shows that the cyclohexylamine derivative has the structure shown in formula (I).

Example 2

Preparing cyclohexylamine derivatives of formula (I):

(1) Slowly and dropwise adding acrylonitrile into the N- (3-aminopropyl) cyclohexylamine under the conditions of room temperature, nitrogen protection and stirring, wherein the molar ratio of the acrylonitrile to the N- (3-aminopropyl) cyclohexylamine is 2.1:1, dropwise adding for 1.4h, then adding diallylamine as a catalyst, wherein the molar ratio of the catalyst to the N- (3-aminopropyl) cyclohexylamine is 0.075:1, controlling the temperature to reflux at 70 ℃ for 21h, after the reaction is finished, distilling under reduced pressure at 4kPa and 35 ℃ to recover unreacted acrylonitrile and catalyst diallyl amine, filtering and separating the product, and drying in vacuum at 60 ℃ to constant weight to obtain an intermediate.

(2) Mixing the intermediate with Rh/Al₂ O₃ A supported catalyst (Rh loading of 3.5 wt%) was mixed with tetrahydrofuran, wherein the catalyst amount was 1.75wt% of the intermediate; the concentration of tetrahydrofuran was 35wt% based on the total weight of intermediate and tetrahydrofuran; then introducing hydrogen to maintain the system pressure at about 8MPa, carrying out hydrogenation reaction for 4.5h at the temperature of 140 ℃ and the pressure of 8MPa, carrying out reduced pressure distillation at the temperature of 4kPa and 35 ℃ to recover tetrahydrofuran after the reaction is finished, then carrying out filtration separation, and finally carrying out vacuum drying at the temperature of 70 ℃ to constant weight to obtain the cyclohexylamine derivative product.

Example 3

Preparing a cyclohexylamine derivative of formula (I):

(1) Slowly and dropwise adding acrylonitrile into the N- (3-aminopropyl) cyclohexylamine under the conditions of room temperature, nitrogen protection and stirring, wherein the molar ratio of the acrylonitrile to the N- (3-aminopropyl) cyclohexylamine is 2.2:1, dropwise adding for 1.8h, then adding triallylamine as a catalyst, wherein the molar ratio of the catalyst to the N- (3-aminopropyl) cyclohexylamine is 0.1:1, controlling the temperature to carry out reflux reaction at 80 ℃ for 24 hours, after the reaction is finished, carrying out reduced pressure distillation at 6kPa and 45 ℃ to recover unreacted acrylonitrile and catalyst triallylamine, filtering and separating the product, and drying the product in vacuum at 60 ℃ to constant weight to obtain an intermediate.

(2) Mixing the intermediate with Rh/Al₂ O₃ A supported catalyst (Rh loading of 4 wt%) was mixed with tetrahydrofuran, with the catalyst amount being 2wt% of the intermediate; the concentration of the tetrahydrofuran is preferably 40wt% based on the total weight of the intermediate and the tetrahydrofuran, then hydrogen is introduced to maintain the system pressure at about 10MPa, hydrogenation reaction is carried out for 5h under the conditions that the temperature is 160 ℃ and the pressure is 10MPa, the tetrahydrofuran is recovered by reduced pressure distillation at 6kPa and 45 ℃ after the reaction is finished, then filtration and separation are carried out, and finally vacuum drying is carried out at 80 ℃ to constant weight, so as to obtain the cyclohexylamine derivative product.

Example 4

Preparation of an epoxy resin composition:

1) According to the bisphenol A type epoxy resin, DER 331: the bisphenol F type epoxy resin is DER 354: epoxy diluent 622: the mass ratio of the silane coupling agent KBM-403 is 1:0.1:0.02, and obtaining the component A epoxy resin;

2) Mixing the cyclohexylamine derivative prepared in example 1 and dicyandiamide powder in proportion, mixing the mixture for 2 times by a three-roll mill, adding the mixed product into alicyclic amine IPDA in proportion at 20 ℃, mixing the mixture, dispersing the mixture for 1 hour till the mixture is completely dissolved to form a uniform and transparent mixed solution, adding polyether amine D230, and uniformly mixing the mixture, wherein the mixing mass ratio of the cyclohexylamine derivative to dicyandiamide to alicyclic amine IPDA to polyether amine D230 is 1:2:4:3, obtaining the component B epoxy curing agent with the viscosity of 50cps;

3) The epoxy resin of the component A and the epoxy curing agent of the component B are mixed according to the mass ratio of 100:30, the mixing temperature is 20 ℃, and the mixing time is 10min, thus obtaining the epoxy resin composition.

The prepared epoxy resin composition is cured at 80 ℃ for 30min to prepare resin performance test sample bars, and the interface performance test results of the resin and the composite material are shown in Table 2.

Example 5

Preparation of an epoxy resin composition:

1) According to the bisphenol A type epoxy resin, DER 331: the bisphenol F type epoxy resin is DER 354: epoxy diluent 692: the mass ratio of the silane coupling agent KBM-403 is 1:0.6:0.15:0.03, and obtaining the component A epoxy resin;

2) The cyclohexylamine derivative prepared in example 2 and dicyandiamide powder were mixed in a mass ratio of 1:4, mixing for 3 times by a three-roll grinder, and then mixing the mixed product at 40 ℃ according to a mass ratio of 1:7, adding the mixture into alicyclic amine HMDA, mixing, dispersing for 2 hours until the mixture is completely dissolved to form a uniform and transparent mixed solution, then adding polyether amine 8100, and uniformly mixing, wherein the mixing mass ratio of the cyclohexylamine derivative to dicyandiamide to alicyclic amine HMDA to polyether amine is 1:3:5:4; to obtain the component B epoxy curing agent with the viscosity of 120cps;

3) The component A, namely epoxy resin, the component A and the component B, namely an epoxy curing agent, are mixed according to the mass ratio of 100:35 at a mixing temperature of 25 ℃ for 20min to obtain the epoxy resin composition.

The prepared epoxy resin composition is cured at 90 ℃ for 20min to prepare a resin performance test sample strip, and the results of the resin and composite material interface performance test are shown in Table 2.

Example 6

Preparation of epoxy resin composition:

1) According to the bisphenol A type epoxy resin, DER 331: the bisphenol F type epoxy resin is DER 354: epoxy diluent 748: the mass ratio of the silane coupling agent KBM-403 is 1:0.4:0.2:0.04 to obtain the component A epoxy resin;

2) Mixing the cyclohexylamine derivative prepared in example 3 and diaminodiphenyl sulfone solid powder according to a ratio, mixing for 4 times by a three-roll mill, adding the mixed product intoalicyclic amine 1,3-BAC at 60 ℃, mixing, dispersing for 3h until complete dissolution to form a uniform and transparent mixed solution, adding polyether amine 8100, and uniformly mixing, wherein the mixing mass ratio of the cyclohexylamine derivative to diaminodiphenyl sulfone,alicyclic amine 1,3-BAC and polyether amine T403 is 1:4:6:5; the component B of the epoxy curing agent with the viscosity of 200cps is obtained;

3) The component A, namely epoxy resin, the component A and the component B, namely an epoxy curing agent, are mixed according to the mass ratio of 100:40, at a mixing temperature of 30 ℃ for 30min to obtain the epoxy resin composition.

The prepared epoxy resin composition is cured at 100 ℃ for 10min to prepare a resin performance test sample strip, and the results of the resin and composite material interface performance test are shown in Table 2.

Example 7

Preparation of epoxy resin composition:

1) According to the bisphenol A type epoxy resin, DER 331: epoxy diluent 622: the mass ratio of the silane coupling agent KBM-403 is 1:0.1:0.02, and obtaining the component A epoxy resin;

2) Mixing the cyclohexylamine derivative prepared in the example 1 and dicyandiamide powder according to a ratio, mixing the mixture for 2 times by a three-roll mill, adding the mixed product into alicyclic amine IPDA according to a ratio at 20 ℃, dispersing the mixture for 1 hour till the mixture is completely dissolved to form a uniform and transparent mixed solution, adding polyether amine D230, and uniformly mixing the mixture, wherein the mixing mass ratio of the cyclohexylamine derivative to dicyandiamide to alicyclic amine IPDA to polyether amine D230 is 1:2:4:3, obtaining the component B epoxy curing agent with the viscosity of 50cps;

3) The epoxy resin of the component A and the epoxy curing agent of the component B are mixed according to the mass ratio of 100:20 at a mixing temperature of 20 ℃ for 10min to obtain the epoxy resin composition.

Comparative example 1

The difference from example 5 is that: the cyclohexylamine derivative in the epoxy curing agent B is directly replaced by cyclohexylamine, and other steps are completely the same. The resin molding and performance test conditions were the same as in example 5, and the results are shown in Table 2.

Comparative example 2

The difference from the example 5 is that: and the cyclohexylamine derivative in the epoxy curing agent B is replaced by an intermediate shown in a formula (II), and other steps are completely the same. The resin molding and performance test conditions were the same as in example 5, and the results are shown in Table 2.

Comparative example 3

The difference from example 5 is that: the component B epoxy curing agent does not contain a cyclohexylamine derivative, and dicyandiamide and alicyclic amine HMDA are directly mixed according to the mass ratio of 1:7, mixing and other steps are completely the same. The resin molding and performance test conditions were the same as in example 5, and the results are shown in Table 2.

Comparative example 4

The difference from the example 5 is that: the component B does not contain a cyclohexylamine derivative and a dicyandiamide curing agent, and the mass ratio of the polyether amine to the alicyclic amine HMDA is 3:1 and the other steps are completely the same. The resin molding and performance test conditions were the same as in example 5, and the results are shown in Table 2.

TABLE 2 results of performance testing of epoxy compositions of examples and comparative examples

As can be seen from comparison of performance data of the examples and the comparative examples in the table 2, after the cyclohexylamine derivative is added in the examples, the gel time is shortened under the condition of temperature rise of 80 ℃, which indicates that the cyclohexylamine derivative and the latent curing agent generate activation and the reaction activity is improved; the glass transition temperature shows that the heat resistance of the resin is obviously improved by introducing the cyclohexylamine derivative and the latent curing agent; in addition, the elongation at break and the fracture toughness of the epoxy resin are obviously improved, which shows that the toughness of the resin matrix is obviously improved.

Claims

1. The cyclohexylamine derivative has a structure shown in a formula (I), and simultaneously contains primary amine, secondary amine and tertiary amine groups:

2. a method for preparing the cyclohexylamine derivative according to claim 1, characterized by comprising the steps of:

(2) And (2) mixing the intermediate prepared in the step (1) with a solvent and a supported rhodium catalyst, then introducing hydrogen to carry out hydrogenation reaction, after the reaction is finished, carrying out reduced pressure distillation to recover ethanol, and then filtering and drying to obtain the cyclohexylamine derivative shown in the formula (I).

3. The method of claim 2, wherein: in the step (1), the molar ratio of the acrylonitrile to the N- (3-aminopropyl) cyclohexylamine is (1.8-2.4): 1, preferably (2-2.2): 1;

preferably, when the acrylonitrile is mixed with the N- (3-aminopropyl) cyclohexylamine, the acrylonitrile is added into the N- (3-aminopropyl) cyclohexylamine, more preferably, the acrylonitrile is added in a continuous feeding mode, further preferably in a dropwise feeding mode, and the feeding time is 1-1.8h; the feed time is included in the reaction time;

in the step (1), the allylamine catalyst is one or more selected from the group consisting of monoallylamine, diallylamine and triallylamine, preferably monoallylamine;

preferably, the molar ratio of the allyl amine catalyst to the N- (3-aminopropyl) cyclohexylamine is (0.01-2): 1, preferably (0.05-0.1): 1;

in the step (1), the reaction is carried out at the temperature of 40-100 ℃, preferably 60-80 ℃ for 12-36 hours, preferably 18-24 hours; the reaction is preferably carried out under reflux;

the preferable conditions of the reduced pressure distillation are that the pressure is 2-6kPa, and the temperature is 25-45 ℃;

the inert gas is selected from argon or nitrogen, preferably argon;

in the step (2), the rhodium content of the supported rhodium catalyst is 2-7wt%, preferably 3-4wt%, based on the total weight of the supported rhodium catalyst;

preferably, the supported rhodium catalyst is added in an amount of (0.5-5) wt%, preferably (1.5-2) wt% of the intermediate;

in the step (2), the solvent is selected from one or more of cyclohexane, tetrahydrofuran, dichloromethane, cyclohexylamine, methanol, isopropanol, ethanol and n-butanol, and tetrahydrofuran is more preferable;

preferably, the solvent is used in an amount of 20 to 60wt%, more preferably 30 to 40wt%, based on the total weight of the intermediate and the solvent;

in the step (2), the introduction amount of the hydrogen is controlled by the reaction pressure, namely the hydrogenation reaction pressure is maintained in a required range by adjusting the introduction amount of the hydrogen;

in the step (2), the reaction is carried out under the pressure of 4-12MPa (absolute pressure), preferably 6-10MPa (absolute pressure), at the temperature of 100-180 ℃, preferably 120-160 ℃ and for 2-6h, preferably 4-5h.

4. An epoxy resin composition is characterized by comprising an A-component epoxy resin and a B-component epoxy curing agent;

the A component comprises at least one epoxy resin;

the component B comprises:

b1 the cyclohexylamine derivative of claim 1 or the cyclohexylamine derivative prepared by the process of claim 2 or 3;

b2 at least one latent amine curing agent;

b3 at least one alicyclic amine;

b4 at least one polyetheramine.

5. The epoxy resin composition as claimed in claim 4, wherein the mass ratio of the A-component epoxy resin to the B-component epoxy curing agent is 100: (20-50), preferably 100: (30-40);

the viscosity of the B component epoxy curing agent is 20-1000cps, preferably 50-200cps;

the dosage of B1-B4 in the component B epoxy curing agent is according to the cyclohexylamine derivative shown in formula (I): latent amine curing agent: alicyclic amine: the mass ratio of the polyether amine is 1: (2-6): (4-8): (3-6), preferably 1: (2-4): (4-6): (3-5).

6. The epoxy resin composition according to claim 4 or 5, wherein the epoxy resin is selected from the group consisting of one or more of bisphenol A type epoxy resins, bisphenol F type epoxy resins, alicyclic glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, preferably one or more of bisphenol A type epoxy resins, bisphenol F type epoxy resins;

the alicyclic amine is selected from one or more of diaminodicyclohexylmethane, isophorone diamine, methylcyclohexanediamine, dimethyldiaminodicyclohexylmethane, 1,3 cyclohexyldimethylamine, preferably one or two of diaminodicyclohexylmethane and isophorone diamine;

7. The epoxy resin composition of any of claims 4-6, wherein the A component further optionally comprises an epoxy diluent, a silane coupling agent;

preferably, the epoxy diluent is selected from 1,4-butanediol diglycidyl ether, alkyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, glycerol glycidyl ether and the like in combination, preferably 1,4-butanediol diglycidyl ether, benzyl glycidyl ether in combination of one or two;

preferably, the silane coupling agent is selected from a combination of one or more of KH550, KH560, KH570, KBM403, preferably a combination of one or more of KH550, KH560, KBM 403;

preferably, in the composition of the A component, the ratio of epoxy resin to epoxy diluent is as follows: the mass ratio of the silane coupling agent is (1-3): (0.05-0.3): (0.01-0.1), preferably (1.4-1.8): (0.1-0.2): (0.02-0.04).

8. A method for preparing the epoxy resin composition according to any one of claims 4 to 7, comprising the steps of:

3) Mixing the epoxy resin of the component A with the epoxy curing agent of the component B to obtain an epoxy resin composition;

preferably, when the cyclohexylamine derivative in the step 2) is mixed with the latent amine curing agent, the mixture is mixed by a three-roll grinder for 2 to 4 times; when the mixture is mixed with alicyclic amine, a high-speed stirrer is adopted to stir and disperse for 1-3h until the mixture is completely dissolved, and uniform and transparent mixed solution is formed;

preferably, the mixing operation in the step 3) is carried out, wherein the mixing temperature is 20-30 ℃, and the mixing time is 10-30min.

9. Use of the epoxy resin composition according to any one of claims 4 to 7 as a resin matrix for liquid molding composites, preferably in the field of automotive light weight composites;

preferably, the liquid forming method comprises Resin Transfer Molding (RTM), wet molding (WCM), winding forming and pouring forming;

10. An epoxy resin product prepared by curing the epoxy resin composition according to any one of claims 4 to 7, wherein the glass transition temperature is 80 to 140 ℃, the tensile strength is 70 to 100MPa, the flexural strength is 120 to 160MPa, and the elongation at break is 3 to 5%.